Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F224/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
  • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
  • Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
  • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
  • Y10T428/1397—Single layer [continuous layer]

Definitions

• the present invention relates to a process for radically curing a composition
• a composition comprising a methacrylate containing compound (a1) and a monomer copolymerizable with said methacrylate containing compound in the presence of tertiary aromatic amine (c) and a peranhydride (d).
• a composition comprising a methacrylate functional resin diluted in styrene as reactive diluent and pre-accelerated with a tertiary aromatic amine can be efficiently radical copolymerized (cured) with a peranhydride.
• Styrene is often used as reactive diluent.
• styrene is a very effective reactive diluent, since styrene has a high copolymerization ability and a good cutting power (viscosity of the composition can be lowered efficiently when using styrene as comonomer), styrene has however an undesirable odour which is even more hindering since styrene is volatile.
• the object of the present invention is to provide a process with less odour and with high curing efficiency (as demonstrated by short gel time, short peak time and/or high peak temperature).
• composition comprises a compound (b) according to formula (1) as monomer copolymerizable with said methacrylate containing compound
• R 1 and R 2 each individually represent H, C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 alkylaryl or C 7 -C 20 arylalkyl;
• X ⁇ O, S or NR 3 whereby R 3 H, C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 alkylaryl, C 7 -C 20 arylalkyl, part of a polymer chain or attached to a polymer chain.
• compound (b) has a good cutting power in compositions comprising a methacrylate containing compound (a1) with a number-average molecular weight M n of at least 600 Dalton.
• the process of the present invention can result in a higher glass transition temperature (T g ) and/or higher crosslink density of the cured network and thus an improved cured network can be obtained.
• An additional advantage of using compounds according to formula (1) is that they can be prepared from biobased raw materials.
• the radical curing process according to the invention in particular comprises
• the composition comprises a compound (b) according to formula (1).
• Such compounds can be commercially obtained from for example TCI Europe and can be prepared with the method as described for example by Gary M. Ksander, John E. McMurry, and Mark Johnson, “A Method for the Synthesis of Unsaturated Carbonyl Compounds” in J. Org. Chem. 1977, vol. 42, issue 7, pages 1180-1185, or by Mitsuru Ueda and Masami Takahasi, “Radical-Initiated Homo- and Copolymerization of ⁇ -Methyl- ⁇ -Butyrolactone” in J. Pol. Sci. A 1982, vol. 20, p. 2819-2828.
• n is 1 or 2. More preferably, n is 1.
• X is preferably O.
• R 1 and R 2 each individually represent H or CH 3 . More preferably, R 1 and R 2 are both H or R 1 is H and R 2 is CH 3 .
• the composition comprises a compound (b) according to formula (2)
• R 1 is H or CH 3 .
• the composition preferably comprises methacrylate containing compounds (a1) with a number-average molecular weight M n of at least 225 Dalton.
• M n the number-average molecular weight
• the methacrylate containing compounds (a1) have a number-average molecular weight M n of at most 10000 Dalton.
• the methacrylate containing compound (a1) present in the composition has a methacrylate functionality of at least 2.
• methacrylate functionality is defined as the number of CH 2 ⁇ CMeCOO— per molecule of methacrylate containing compound.
• the composition comprises a mixture of methacrylate containing compounds (a1) which mixture has an average methacrylate functionality higher than 1, preferably higher than 1.5 and more preferably higher than 1.7.
• the upper limit of the average functionality is not critical.
• the average functionality is lower than 4, more preferably lower than 3.
• the methacrylate containing compounds (a1) further contain at least one ether group, at least one hydroxyl group and/or at least one urethane group.
• the methacrylate containing compound (a1) further contains an ether group.
• a preferred methacrylate containing compound (a1) further containing an ether group is an alkoxylated bisphenol A dimethacrylate.
• the methacrylate containing compound (a1) further contains an ether group and a hydroxyl group.
• a methacrylate containing compound (a1) further containing an ether group and a hydroxyl group is preferably obtained by reaction of an epoxy oligomer or polymer with methacrylic acid or methacrylamide, preferably with methacrylic acid.
• a preferred methacrylate containing compound (a1) further containing an ether group and a hydroxyl group is a bisphenol A glycerolate dimethacrylate.
• the methacrylate containing compound (a1) further contains an urethane group.
• a methacrylate containing compound (a1) further containing an urethane group is preferably obtained by reaction of a hydroxyl functional methacrylate with an isocyanate.
• the methacrylate containing compound (a1) present in the composition may also be a mixture of methacrylate containing compounds as described above.
• the composition may further comprise an ethylenically unsaturated compound (a2) with a number-average molecular weight M n of at most 300 Dalton.
• a2 ethylenically unsaturated compound
• Non-limiting preferred examples are styrene, ⁇ -methylstyrene, vinyltoluene, hydroxyethylmethacrylate, hydroxypropylmethacrylate, methyl methacrylate, ethyl methacrylate, hydroxybutylvinylether, N-vinylcaprolactam, N-vinyl pyrrolidone, laurylmethacrylate or mixtures thereof.
• the amount of compound (b) relative to the total amount of compounds (a) and (b) is preferably at least 1 wt. %, more preferably at least 5 wt. %, even more preferably at least 10 wt. % and even more preferably at least 25 wt. %.
• the amount of compounds (a) is the total amount of compounds (a1) and (a2).
• the amount of compound (b) relative to the total amount of compounds (a) and (b) is preferably at most 99 wt. %, more preferably at most 95 wt. %, more preferably at most 90 wt. %, even more preferably at most 70 wt. % and even more preferably at most 65 wt. %.
• the amount of compound (b) relative to the total amount of compounds (a) and (b) is from 1 to 95 wt. %, and more preferably from 25 to 65 wt. %.
• tertiary aromatic amine has the following structure:
• R4 H, C 1 -C 5 alkyl, O(C 1 -C 5 )alkyl; R5 and R6 are independently selected from C1-C4 alkyl optionally substituted with hydroxyl or (poly) ether groups.
• R4 H or CH3.
• R5 and/or R6 are CH3, C2H5, C2H4OH, C3H7 and CH2CH(OH)CH3.
• N,N-ethoxylated or N,N-propoxylated anilines respectively ethoxylated or propoxylated toluidines may suitably be used and are considered to be encompassed in the group of suitable tertiary aromatic amines. It is obvious that especially the hydroxyl functional tertiary aromatic amines may be incorporated in a polymer. Preferred aromatic amines are the anilines and the toluidines.
• the amount of tertiary aromatic amine (compound (c)) relative to the total amount of compound (a) and compound (b) is preferably from 0.01 to 10 wt. %, more preferably from 0.1 to 5 wt. %.
• a very suitable example of an aromatic peranhydride is dibenzoyl peroxide.
• a very suitable example of an alipahtic peranhydride is dilauroyl peroxide.
• the amount of peranhydride (compound (d)) relative to the total amount of compounds (a) and (b) is preferably from 0.01 to 30 wt. %, more preferably from 0.1 to 10 wt. %.
• the molar amount of peranhydride (compound (d)) relative to the molar amount of tertiary aromatic amine (compound (c)) is preferably from 0.05 to 10, more preferably from 0.1 to 5.
• the composition preferably further comprises a radical inhibitor.
• radical inhibitors are preferably chosen from the group of phenolic compounds, benzoquinones, hydroquinones, catechols, stable radicals and/or phenothiazines.
• the amount of radical inhibitor that can be added may vary within rather wide ranges, and may be chosen as a first indication of the gel time as is desired to be achieved.
• radical inhibitors that can be used in the compositions according to the invention are, for instance, 2-methoxyphenol, 4-methoxyphenol, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butylphenol, 2,4,6-trimethyl-phenol, 2,4,6-tris-dimethylaminomethyl phenol, 4,4′-thio-bis(3-methyl-6-t-butylphenol), 4,4′-isopropylidene diphenol, 2,4-di-t-butylphenol, 6,6′-di-t-butyl-2,2′-methylene di-p-cresol, hydroquinone, 2-methylhydroquinone, 2-t-butylhydroquinone, 2,5-di-t-butylhydroquinone, 2,6-di-t-butylhydroquinone, 2,6-dimethylhydroquinone, 2,3,5-trimethylhydroquinone, catechol, 4-t-butoxyphenol,
• the amount of radical inhibitor in the composition (relative to the total amount of the composition) is in the range of from 0.0001 to 10% by weight. More preferably, the amount of inhibitor in the composition is in the range of from 0.001 to 1% by weight. The skilled man quite easily can assess, in dependence of the type of inhibitor selected, which amount thereof leads to good results according to the invention.
• the process comprises adding the peranhydride to a composition comprising compounds (a1), (b) and (c). Said adding is preferably done by mixing the peranhydride into the composition comprising compounds (a1), (b) and (c).
• the process according to the invention is preferably effected at a temperature in the range of from ⁇ 20 to +150° C., more preferably in the range of from ⁇ 20 to +100° C. and even more preferably in the range of from ⁇ 20 to +40° C.
• the present invention further relates to a multicomponent system comprising a methacrylate containing compound (a1), a monomer copolymerizable with said methacrylate containing compound, a tertiary aromatic amine (c) and a peranhydride (d), wherein the system comprises a compound (b) according to formula (1) as monomer copolymerizable with said methacrylate containing compound
• R 1 and R 2 each individually represent H, C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 alkylaryl or C 7 -C 20 arylalkyl;
• X ⁇ O, S or NR 3 whereby R 3 ⁇ H, C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 alkylaryl, C 7 -C 20 arylalkyl, part of a polymer chain or attached to a polymer chain.
• Preferred compounds (a1), (b) and (c) as well as the amounts are as described above.
• the system may further comprise additional compounds in amounts as described above.
• multicomponent systems means a system with at least two spatially separated components whereby the peranhydride is present in one component that does not comprise radical copolymerizable compounds including compounds (a1) and (b) in order to prevent premature radical copolymerization of the compounds (a1) and (b) prior to the use of the multicomponent system to obtain the cured network.
• at least a peranhydride is added to this composition.
• said adding is done by mixing the peranhydride into the composition comprising compounds (a1) and (b).
• the multicomponent system according to the invention comprises at least two components.
• the multicomponent system comprises at least three components I, II and III, whereby component I consists of a composition comprising compounds (a1) and (b), component II consists of a composition comprising compound (c) and component III comprises the peranhydride (d).
• the system comprises at least two components I and II, whereby component I consists of a composition comprising compounds (a1), (b) and (c) and component II comprises the peranhydride (d).
• the present invention further relates to a thermosetting composition
• a thermosetting composition comprising a methacrylate containing compound (a1), a monomer copolymerizable with said methacrylate containing compound, a tertiary aromatic amine (c), wherein the composition comprises a compound (b) according to formula (1) as monomer copolymerizable with said methacrylate containing compound
• R 1 and R 2 each individually represent H, C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 alkylaryl or C 7 -C 20 arylalkyl;
• X ⁇ O, S or NR 3 whereby R 3 ⁇ H, C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 alkylaryl, C 7 -C 20 arylalkyl, part of a polymer chain or attached to a polymer chain, and the composition comprises (in)organic filler and whereby the composition is curable with a peranhydride.
• Preferred compounds (a1), (b) and (c) as well as the amounts are as described above.
• the system may further comprise additional compounds such as a radical inhibitor in amounts as described above.
• the amount of (in)organic filler relative to the total amount of compounds (a), (b) and (c) is preferably from 10 to 90 wt. %.
• the thermosetting composition comprises fibre as filler. Suitable fillers are aluminium trihydrate, calcium carbonate, mica, glass, microcrystalline silica, quartz, barite and/or talc. These fillers may be present in the form of sands, flours or molded objects, especially in the form of fibers or spheres. Examples of fibres are glass fibres and carbon fibres.
• the present invention further relates to cured objects obtained by the process as described above or obtained by mixing the compounds of the multicomponent system as described above or obtained by curing the thermosetting composition as described above with a peranhydride.
• the present invention further relates to the use of such a cured object in automotive, boats, chemical anchoring, roofing, construction, containers, relining, pipes, tanks, flooring or windmill blades.
• Example 1 was repeated except that instead of MBL the following compounds were used:
• MMA methyl methacrylate
• HPMA 2-hydroxy propyl methacrylate
• LMA Lauryl methacrylate
• Example 1 combined with comparative experiments A1-A5 clearly demonstrate that ⁇ -methylene butyrolactone can suitably be used in combination with a peranhydride/tertiary aromatic amine system as this can result in a tack free curing in the presence of air. This result could not be achieved with (meth)acrylates nor styrene.
• MBL melting point
• Example 5 combined with the comparative experiments clearly show that the combination of a good cutting power (indicated by the low viscosity values), no volatiles (indicated by the high boiling point), high reactivity (indicated by the gel time data), good structural integrity (no cracks) can only be achieved by using formulations according to the invention.
• Example 5 The castings of Example 5 and comparative experiment C1 were subjected to DMA analysis according to ASTM D5026. The results are:
• Example 5 Modulus @ 23° C.: 3089 MPa; Tg 112° C.
• Example 6 5 g MBL and 5 g styrene were added to 40 g Daron XP-45 (an epoxy methacrylate resin). Next 1 g NL-64-10P (10% N,N-dimethyl aniline solution, Akzo Nobel) was added and after stirring for 5 min 1 g Perkadox CH 50 L was added. The mixture was poured in an aluminum dish in order to prepare a 4 mm thick casting. After standing at room temperature for 3 hrs the casting was post-cured in an oven at 150 C for an additional 4 hrs. Next the casting was used for a dynamic mechanical analysis (DMA) measurement.
• DMA dynamic mechanical analysis
• the increase in Tg by using formulations according to the invention is already surprising.
• the increase in Tg especially in combination with the rubber modulus indicates a very surprising feature of formulations according to the invention namely that by using a formulation according to the invention the x-link density increases being a strong indication of a better formation of cured networks.

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• Medicinal Chemistry (AREA)
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• Organic Chemistry (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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• 2012
  • 2012-03-29 WO PCT/EP2012/055667 patent/WO2012130960A1/fr not_active Ceased
  • 2012-03-29 BR BR112013024927A patent/BR112013024927A2/pt not_active IP Right Cessation
  • 2012-03-29 CN CN201280027165.7A patent/CN103596995A/zh active Pending
  • 2012-03-29 EP EP12711168.0A patent/EP2691427B1/fr not_active Not-in-force
  • 2012-03-29 JP JP2014501627A patent/JP2014509672A/ja active Pending
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